The synthesis of 1,8-dihydroxynaphthalene-derived natural products: palmarumycin CP1, palmarumycin CP2, palmarumycin C11, CJ-12,371, deoxypreussomerin A and novel analogues

Ragot, Jacques P.; Steeneck, Christoph; Alcaraz, Marie‐Lyne; Taylor, Richard J. K.

doi:10.1039/a901076i

Cited by 67 publications

(42 citation statements)

References 24 publications

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“…Selective mono-demethylation of 5 with (CH3)3SiI under ambient condition generated only the 8-methoxy analogue (6b) of palmarumycin CP17 (73% yield), but not the desired palmarumycin CP17 (6a) (Scheme 2). However, demethylation of 5 with (CH3)3SiI at 50 °C unexpectedly resulted in ring A aromatization and acetal cleavage to afford binaphthyl ether 7, which was the same as the case reported in the reference (Scheme 2) [31,32]. The NaBH4 reduction of 5 produced 5,8-dimethoxy CJ 12372 (8) in 97% yield (Scheme 2); however, demethylation of 8 with (CH3)3SiI and BBr3, in an attempt to prepare CJ 12372, proved unsuccessful.…”

Section: Synthesis Of Palmarumycin Cp 17 and Its Methoxy Analoguessupporting

confidence: 55%

“…Total syntheses of type A spirobisnaphthalenes have been achieved via four different approaches based on the different construction protocols of the core spiroketal structure. These include a biomimetic synthesis by oxidative cyclization to the binaphthyl ether [29,30], direct acetalization [31,32], a silver-mediated cationic cyclization following Suzuki-Miyamura cross-coupling [33], and a Diels-Alder approach in combination with the biomimetic oxidative cyclization of naphthyl phenyl ether [16]. Although the total syntheses of a range of similar palmarumycins, including CP 1 , CP 2 and CJ-12371, was accomplished by direct acetalization as the key step [31][32][33][34][35], the existence of the sensitive 8-hydroxyl or 8-chlorine substituents found in type A spirobisnaphthalenes such as CJ 12372, ascochytain, palmarumycin B 6 , CP 17 , and CP 18 offer a new challenge.…”

Section: Synthesis Of Palmarumycin Cp17 and Its Methoxy Analoguesmentioning

confidence: 99%

“…These include a biomimetic synthesis by oxidative cyclization to the binaphthyl ether [29,30], direct acetalization [31,32], a silver-mediated cationic cyclization following Suzuki-Miyamura cross-coupling [33], and a Diels-Alder approach in combination with the biomimetic oxidative cyclization of naphthyl phenyl ether [16]. Although the total syntheses of a range of similar palmarumycins, including CP 1 , CP 2 and CJ-12371, was accomplished by direct acetalization as the key step [31][32][33][34][35], the existence of the sensitive 8-hydroxyl or 8-chlorine substituents found in type A spirobisnaphthalenes such as CJ 12372, ascochytain, palmarumycin B 6 , CP 17 , and CP 18 offer a new challenge. In order to gain insights into the structure-activity relationships of both natural and non-natural spirobisnaphthalenes, we have used the direct acetalization approach, following the synthetic protocol of preussomerin G and I [31,32,36], to complete the total synthesis of palmarumycin CP 17 (6a), its 8-methoxy analogue (6b), and 5,8-dimethoxy CJ 12372 (8) as well as the other 6-methoxy,7-methoxy and 6,7-dimethoxy spirobisnaphthalene derivatives (18)(19)(20) (Schemes 2-4).…”

Section: Synthesis Of Palmarumycin Cp17 and Its Methoxy Analoguesmentioning

confidence: 99%

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Total Synthesis and Antifungal Activity of Palmarumycin CP17 and Its Methoxy Analogues

et al. 2016

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Total synthesis of naturally occurring spirobisnaphthalene palmarumycin CP 17 and its methoxy analogues was first achieved through Friedel-Crafts acylation, Wolff-Kishner reduction, intramolecular cyclization, ketalization, benzylic oxidation, and demethylation using the inexpensive and readily available methoxybenzene, 1,2-dimethoxybenzene and 1,4-dimethoxybenzene and 1,8-dihydroxynaphthalene as raw materials. Demethylation with (CH 3 ) 3 SiI at ambient temperature resulted in ring A aromatization and acetal cleavage to give rise to binaphthyl ethers. The antifungal activities of these spirobisnaphthalene derivatives were evaluated, and the results revealed that 5 and 9b exhibit EC 50 values of 9.34 µg/mL and 12.35 µg/mL, respectively, against P. piricola.

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Section: Synthesis Of Palmarumycin Cp 17 and Its Methoxy Analoguessupporting

confidence: 55%

Section: Synthesis Of Palmarumycin Cp17 and Its Methoxy Analoguesmentioning

confidence: 99%

Section: Synthesis Of Palmarumycin Cp17 and Its Methoxy Analoguesmentioning

confidence: 99%

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Total Synthesis and Antifungal Activity of Palmarumycin CP17 and Its Methoxy Analogues

et al. 2016

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“…1,8-ND was synthesized from 1,8-naphthosultone (Sigma-Aldrich) as previously described 28 (for an alternative method of synthesis refer to reference 29). All structures were verified by 1H and 13 C nuclear magnetic resonance (NMR) and mass spectrometry.…”

Section: Methodsmentioning

confidence: 99%

Oxidative modification of citrate synthase by peroxyl radicals and protection with novel antioxidants

Chepelev

Bennitz

Wright

et al. 2009

Journal of Enzyme Inhibition and Medicinal Chemistry

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“…Recently, investigations of analogous compounds of 2 and 4 have been reported and the syntheses of a series of these naturally occurring spiroacetal-bridged compouds were published. [3][4][5][6][7][8][9][10][11] The synthesis of bisepoxide 2 and naphthalene dimer 4 has not yet been published, however, we initially began to synthesize key compounds 1a and 3 for 2 and 4 (Chart 1). In this paper, we describe the first synthesis of cis-and trans-5,8-dihydroxy-5,6,7,8-tetrahydro-1,4-naphthoquinone (1a, 1b) by two routes, and also the first synthesis of racemic triol 3.…”

mentioning

confidence: 99%

Synthesis of cis- and trans-5,8-Dihydroxy-5,6,7,8-tetrahydro-1,4-naphthoquinone.

Arima

Yamada

Takeda

et al. 2001

CHEMICAL & PHARMACEUTICAL BULLETIN

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Sch 49210 (2) is a novel metabolite having antitumor and inhibitory phospholipase D activities and was isolated from a fungal culture broth by Chu et al. in 1994. 1) Compound 2 contains a unique structure, ketobisepoxydecalone with a spiroacetal linkage through a naphthalene moiety. CJ-12, 372 (4) isolated by Sakemi et al. 2) was shown to possess DNA gyrase inhibition activity and is a spiroacetal compound with 1,8-naphtalenediol (5) as compound 2. Recently, investigations of analogous compounds of 2 and 4 have been reported and the syntheses of a series of these naturally occurring spiroacetal-bridged compouds were published.3-11) The synthesis of bisepoxide 2 and naphthalene dimer 4 has not yet been published, however, we initially began to synthesize key compounds 1a and 3 for 2 and 4 (Chart 1). In this paper, we describe the first synthesis of cis -and trans-5,8-dihydroxy-5,6,7,8-tetrahydro-1,4-naphthoquinone (1a, 1b) by two routes, and also the first synthesis of racemic triol 3. Results and Discussion2,3-Dihydro-5,8-dihydroxy-1,4-naphthoquinone (7) was synthesized from naphthazazine (6) as the starting material by applying the procedure 12) developed by Pearson et al. Reduction of 6 by 20 eq of stannous chloride under acidic conditions gave dihydro compound 7 in 90% yield (Chart 2). Diol 7 was used in the following procedure without purification because 7 is unstable to air-oxidation and returns to starting material 6 easily. Diol 7 was then reduced by treatment with large excess (24 eq) of NaBH 4 in the presence of a catalytic amount of CeCl 3 13-15) in tetrahydrofuran (THF) at room temperature to afford a mixture of 8a and 8b. Oxidation of a mixture of 8a and 8b using ceric ammonium nitrate (CAN) [16][17][18] as an oxidant in acetonitrile gave a mixture of 1a (cis) and 1b (trans).19) The mixture was separated by column chromatography to give crystals 1a and oil 1b in 34 and 50% yields, respectively (Chart 2). The stereostructures of 1a and 1b were decided as follows. The determination whether 1a and 1b are the cis or trans isomer by 1 H-NMR spectra presented great difficulty because each spectrum exhibits a complicated coupling pattern. Therefore, X-ray analysis of 1a was performed. The ORTEP view of 1a showed a cis diol structure and exhibited interesting stereochemical features as shown in Fig. 1. The cyclohexane ring adopts a half-chair conformation and two carbonyl groups in quinone are above so that they are apart from each cis hydroxyl group. From these results, it was proved that 1a and 1b are correspondent to a cis and trans diol, respectively.In the procedure shown in Chart 2, separation of 1a and 1b by column chromatography was difficult because their Rf values are very close in spite of the short process. We therefore developed another method for 1a and 1b as shown in Chart 3. Methylation of 6 by treatment with Ag 2 O and CH 3 I afforded 9 in 76% yield according to the procedure developed by Pearson and co-workers. 12) At first LiAlH 4 was used as a reducing agent, but 1,4-dihydroxy-5,8-dim...

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The synthesis of 1,8-dihydroxynaphthalene-derived natural products: palmarumycin CP1, palmarumycin CP2, palmarumycin C11, CJ-12,371, deoxypreussomerin A and novel analogues

Cited by 67 publications

References 24 publications

Total Synthesis and Antifungal Activity of Palmarumycin CP17 and Its Methoxy Analogues

Total Synthesis and Antifungal Activity of Palmarumycin CP17 and Its Methoxy Analogues

Oxidative modification of citrate synthase by peroxyl radicals and protection with novel antioxidants

Synthesis of cis- and trans-5,8-Dihydroxy-5,6,7,8-tetrahydro-1,4-naphthoquinone.

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